DD141779A5 - MEANS FOR THE CONTROL OF HARMONY - Google Patents

Description

Means for controlling harmful insects

Field of application of the invention:

The invention relates to a novel means of controlling harmful insects.

Characteristics of the known n technical solutions;

Pesticides are already known in large numbers. Nevertheless, for well-known reasons, there is still a great demand for new, improved insect control agents,

Substituted thio-derivatives of methyl carbamate pesticides are known from US Patents 3,781,331 and 3,794,733. From the BE-PS 860 844 Acylaminothioderivate of Methylcarbamatpestiziden, namely H-f (phosphinyl) -amino3-thio-methylsarbamate known. As far as known, phosphoric acid derivatives of Aminot hi ometh.ylcarbania.tpestiziden have not yet been prepared from cyclic Phosphoramidothioaten.

Object of the invention I ₁

The invention had the object of producing methylcarbamate pesticides whose effectiveness of the effectiveness of the parent compounds against harmful insects at least

equivalent, but usually superior. In particular, methylcarbamate pesticides are to be provided for reduced toxicity to mammals, reduced phytotoxicity and longer residual action,

Explanation of the essence of the invention :

The invention thus provides N- (phosphinyl) amino-thio and I-r (phosphinothioyl) -amino] -thio-methylcarbamate pesticides of the formula:

0 CHo ^x

R_0-C - NS -Ν - P _v ' I

j \ _f ..

R ₁

- .3

0 CH ₃ S-- X II. I Il O- C _N- _P -N-

0 CH ₃ X '0,

_R o-C - NS-NP 1 (CH ₂ )

Ri o

O CH

• X Ό

, ₀ c NS - NP;

Ri (cn,) _k

in which mean:

a radical of the formula: a)

R '

in which Rp, FU and R /, which can be identical or different, each represent a hydrogen or halogen atom, a short-chain alkyl group having 1 to 5 carbon atom (s), a short-chain alkoxy radical having 1 to 5 carbon atom (s), inclusive a short chain alkylthio radical having 1 to 5 inclusive carbon atom (s), a dialkylamino radical whose alkyl moieties may be the same or different and having 1 to 3 inclusive carbon atoms, or a radical of the formula -NeCHN (CEL) ₂ ; b)

B-C = N-i A

wherein A and B, which may be the same or different and each have a short chain alkyl group having 1 to 5 inclusive carbon atom (s), a short chain alkylthio group having 1 to 5 inclusive carbon atom (s), a monocyanosubstituted alkylthio group having 1 to 5 inclusive carbon atom (s ), a phenylthio radical whose phenyl moiety is optionally substituted by 1 to 3 (same or different) substituents consisting of halogen atoms or. is a cyano radical, an alkoxy radical having 1 to 5 inclusive carbon atom (s), a phenyl radical or a hydrogen atom, it being understood that in the case that B is a hydrogen atom, A of the formula: -

R ₆ -CSR ₅ R ₇

corresponds, in which mean:

Rc is an alkyl radical having 1 to 3 carbon atoms inclusive or a phenyl radical;

Rr is an alkyl radical containing 1 to 3 carbon atoms inclusive; and

an alkyl radical having 1 to 3 carbon atoms inclusive or a radical of the formula -SR ₈ , in which R _{Q is} an alkyl radical corresponding to the alkyl radical represented by Rc, or

c and Rg, together with the atoms to which they are attached, contain a heterocyclic ring of the formula containing two sulfur atoms;

in which η = 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals (e); or A and B together with the carbon atom to which they are attached, a heterocyclic ring containing two sulfur atoms of the formula:

107

wherein ra = 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radical (s), or c)

R _{1 is} a short-chain alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted short-chain alkyl radical or a cycloalkyl radical;

X is an oxygen or sulfur atom;

Y and Y ¹ , which may be the same or different, each represents a short chain alkyl, alkoxy or alkylthio radical, a cycloalkyl radical, an optionally substituted phenyl radical, an optionally substituted phenoxy radical or an optionally substituted thiophenoxy radical;

Z.sup.1 to Zg, which may be the same or different, each represents a hydrogen atom or a methyl or ethyl radical;

R is a hydrogen or halogen atom or a short ¹

chain " ¹ IlCyI or alkoxy radical; k = 0 or 1 and ρ = 3 or 4.

Examples of "short-chain alkoxy radicals" are methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy

to understand residues or their isomers. By "short-chain alkylthio radicals" are meant, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio or pentylthio radicals or their isomers.

By "short-chain alkyl radicals ¹¹ are, for example, methyl, ethyl, propyl, butyl or pentyl radicals or their isomers." Cycloalkyl radicals "are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl radicals, which are optionally denoted by methyl, ethyl - or propyl may be substituted to a total of 9 carbon atoms to understand.

By "phenyl-substituted alkyl radicals" are meant, for example, benzyl, phenethyl, phenpropyl, phenbutyl or phenpentyl radicals or their isomers.

"Substituted phenyl radicals" are, for example, phenyl radicals substituted by short-chain alkyl or alkoxy radicals, halogen atoms, nitro radicals or cyano radicals. Here, the phenyl radicals may also carry combinations of substituents and, for example, 4-propyl-2-methyl, 2-chloro-4-methyl, 3,4-Diäthoxy- or 3-cyano-4-äthoxyphenylresten exist, in practice "Substituted phenyl" limited to a total of 10 carbon atoms, so that the limit forms, for example, the 4-Isobutylphenylrest.

"Substituted phenoxy radicals" are to be understood as meaning phenoxy radicals substituted by short-chain alkyl or alkoxy radicals, halogen atoms, hydroxyl radicals or cyano radicals. The phenoxy radicals in question can also carry combinations of substituents and, for example, from 4-propyl

- S «·

2-methyl, 2-chloro-4-methyl, 3,4-diethoxy or 3-cyano-4-ethoxyphenoxy exist. The substituted phenoxy radicals are limited to a total of 10 carbon atoms, so that the limit forms, for example, the 4-I-sobutylphenoxy radical.

By "substituted thiophenoxy" are meant by short-chain alkyl or alkoxy, halogen, nitro or cyano substituted thiophenoxy. These may also carry combinations of substituents and for example consist of 4-propyl-2-methyl, 2-chloro-4-methyl or 3,4-Diäthoxythiophenoxyresten. The substituted Thiophenoxyreste are limited to a total of 10 carbon atoms, so that, for example, forms the limit of 4-Isobutylthiophenoxyrest.

The novel N - [(phosphinyl) amino] thio and N - [(phosphinothioyl) amino] thiomethylcarbamate pesticides of the formula I according to the invention are obtained by reacting a suitable ethyl carbamate precursor with an N- (halothio) phosphinic acid amide. Schematically, this reaction can be represented as follows:

0 CH ₃ l / V 0 CH,

S - R ₁

N-H + Cl-S - N ~ R} R-O-C-N-S-N-P

Ri Y ¹ R ₁ Y

I Γ Il

In the formula scheme, the radicals R, R ^, X, Y and Y ^{1 have} the meaning indicated.

The reaction is carried out in the cold, preferably at a temperature of -20 ° to +25 ⁰ C, in the presence of a suitable acid acceptor and an inert organic medium. Examples of suitable acid acceptors are trialkylamines, eg triethylamine, pyridine and lutidine. Examples of organic reaction media are dimethylformamide, diethyl ether, hexane, tetrahydrofuran and acetonitrile. When using non-polar and slightly polar solvents, copper (i) chloride and aluminum chloride can also be used to catalyze the reaction.

The compounds of the formulas I, I ¹ , I "and I" ¹ are recovered and purified in the usual manner. For this one uses a filtration, a solvent evaporation, chromatographic Ve'rfahren and / or a crystallization. Some of the compounds are obtained in crystalline form, others are purified in oily form. The phosphinic acid-N-chlorothioamide of formula II is obtained by reacting the corresponding phosphinic acid amides with sulfur dichloride at a temperature of about -20 ° to + 25 ° C in the presence of a suitable acid acceptor and an inert inorganic medium. The phosphinamides are either readily available or can be prepared by known methods, for example according to Houben-Weyl "Methods of Organic Chemistry", Volume 12, Part 2, page 4-13 and Volume 12, Part 1, pages 529 and 595, Georg Thieme Verlag , Stuttgart, Federal Republic of Germany, 1963.

Preferred compounds according to the invention are those of the formulas:

ι N- 0 CH ₃ Il I CH ₃ S- X. Wy p. CZ ₂ (cz ₅ z ₆ ) _k B I A Il I _O ~ C-N- Il ι _C-N-S - X 1 / ° O- 0 Il • N- I / \ B-C A - N i I R X -P

la

O CH ₃ X .0

Il I W /

= N-O-C-N-S-- N-P

I \

Ri. O

(CH ₂ ),

B -C = N-O-C-N-S-N-P

wherein A and B, which may be the same or different, are short chain alkyl radicals having 1 to 5 carbon atoms inclusive, short chain alkylthio radicals having 1 to 5 inclusive carbon atoms, monocyano-substituted alkylthio radicals having 1 to 5 inclusive carbon atoms, phenyl chloride radicals whose phenyl part is replaced by 1 to 3 identical or different substituents, consisting of halogen atoms and short-chain alkyl radicals

with 1 to 4 carbon atoms inclusive, cyano radicals, alkoxy radicals having 1 to 5 inclusive carbon atoms or phenyl radicals, and R 1, X, Y, Y ¹ , Z 1 to Zg, R _Q , k and ρ have the meaning given.

Some of the compounds of formula Ia wherein Y and Y ^{1 are} a radical of the formula:

-o4-

Z ₂

-0-CZ ₃

form in which Z ^ to Zg and k have the meaning given, show an unexpected crystallinity. Thus, for example, the compound N ~ £ [({[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) tert-butylamino thio-methylamino) carbonyl] oxy} ethanimidothioate has extremely crystalline. The crystallinity-related physical properties facilitate the isolation of the reaction product from the reaction mixture. Further, with the highly crystalline compounds, it is possible to provide pesticidal agents in the form of wettable powders. These agents have highly advantageous properties, e.g. a reduced solidification, a high flowability and high concentrations of active ingredients.

Exemplary embodiments:

The following preparation examples illustrate the preparation of reactants required in the preparation of the novel compounds of the formula I according to the invention.

Production Example 1

Reactants 0, O-Diethyl-N- (chiorthio) -N- (n-propyl) phosphoramidothioate:

A solution of 2.98 g (0.014 mol). 0.0-diethyl-n-propylphosphoramidothioate in 10 ml of hexane and 2 ml of triethylamine is added slowly and with stirring into an O ⁰ C cold solution of 1.0 ml (0.016 mol) of sulfur dichloride in 10 ml of hexane. During the strong reaction, a strong precipitation of triethylamine hydrochloride occurs. After addition of another 20 ml of hexane, the reaction mixture is stirred for 30 minutes at a temperature of 0 ° to 5 ° C and then filtered. The resulting filtrate is concentrated by evaporation of the hexane under reduced pressure to a pale yellow oil. The oil contains the desired O, O-diethyl-N- (chlorothio) -n-propylphosphoramidothioate, which can be used for further reaction with N-methylcarbamates.

Production Example 2

Reactants 0, O-diethyl-N- (chlorothio) -N-isopro-

pyl phosphoro ainido thioate:

A solution of 9.95 g (0.0471 mol) of 0,0-diethylisopropylphosphoramidothioate and 6.5 ml of triethylamine is added slowly and with stirring into a cooled solution of 3.0 ml (0.047 mol) of sulfur dichloride and 150 ml of hexane. During the addition and the subsequent 30 min.

Stirring the temperature is kept at 0 ° to 5 ° C. After filtering the reaction mixture, the precipitated salts on the filter are washed with hexane. The filtrate and hexane wash liquor are combined and the hexane is evaporated under reduced pressure. This gives the desired reactant Ο, Ο-Diäthylisopropylphosphoramidothioat in the form of an orange oil. embodiments

The following examples are intended to explain the invention in more detail.

example 1

Preparation of the compound 4- (Dimethylamino) -3,5-cyano-{[(diethoxyphosphinothioyl) -n-propylamino] thio} methylcarbamate:

The crude 0.0-diethyl-N- (chlorothio) -n-propylphosphoramidothioate obtained according to Preparation Example 1 is cooled in an ice bath and treated with 2.79 g (0.013 mol) of 4- (dimethylamino) -3-yl-xylylmethylcarbamate in the form of a solution 20 ml of dimethylformamide containing 2 ml of triethylamine added mixed. After stirring the reaction mixture for 4 hours at a temperature of 25 ⁰ C is diluted with hexane. Then the organic solution is washed with water, dried over anhydrous sodium sulfate and freed from the latter by evaporation of the organic solvents under reduced pressure. The resulting evaporation residue is transferred to a Florisil column. The chromatogram thus obtained is first blended with a solvent mixture of 10 -.% Diethyl ether in petroleum ether, and then developed in petroleum ether with 30% diethyl ether. When collecting the

the eluate which has recently been evolved and the solvents are removed by evaporation under reduced pressure, the desired 4- (dimethylamino) -3,5-yl- ¹ -yl (diethoxy-phosphinothioyl) -n-propylamino-thio-methylcarbamate is obtained in the form of a yellow oil.

The elemental analysis of the compound CLqH ^ λΝ ^ Ο, PSp gives the following values

Calculated: C 49.22 H 7.39 N 9.06 Found: C 49.84 H 7.89 N 8.52.

Beis £ iel_2

Preparation of the compound 2-isopropoxyphenyl - {[(diethylphenylphosphinothioyl) anilino] thio] methylcarbainate:

Part A; Preparation of the reactant 0,0-diethyl-N- (chlorothio) -phenylphosphoramidothioate:

A Lösun.g from 6.69 g (0.0314 mole) of 0,0-Diäthylphenylphosphoramidothioat, 25 ml of ether and 4.4 ml (0.032 mol) of triethylamine is added dropwise during 30 min with stirring to a cooled to -10 ⁰ C solution from 2.0 ml (0.031 mol) of sulfur dichloride and 25 ml of diethyl ether. Thereafter, stirring is continued for 30 minutes in the cold. The precipitate formed in this case is filtered off, whereupon the filter cake is washed with diethyl ether. The original filtrate is combined with the ether wash, whereupon the ether is evaporated at reduced pressure. This gives the desired 0, O-diethyl-N- (chlorothio) phenylphosphoramidothioat in the form of a yellow oil.

- AS -

Part B : 2-Isopropoxyphenyl - ^ [(diethoxyphosphinothioyl) -anilino] thioj methylcarbamate:

The O, O-diathyl-N- (chlorothio) phenyl phosphoramidothioate obtained according to Part A is dissolved in the minimum amount of diethyl ether (about 5 ml), whereupon the ethereal solution is poured into a solution of 6.34 g cooled to ⁰ ° C. (0.030 mol) of 2-Isopropoxyphenylmethylcarbamat and 20 ml of dimethylformamide is added. The resulting reaction mixture is allowed to warm with stirring to a temperature of 25 ° C and then stirred at this temperature for about 4 hours. Thereafter, the mixture is diluted with 100 ml of water and extracted with diethyl ether. After separating the ethereal phase, this is washed with water and dried over anhydrous sodium sulfate

The ether is then removed by evaporation under reduced pressure. The resulting oily evaporation residue is chromatographed through a silica gel column. Development takes place with methylene chloride. After removal of the methylene chloride by evaporation under reduced pressure to obtain 1.02 g of crude product in the form of an amber-colored oil. This is brought from petroleum ether of a Kp range between 30 ° and 60 ⁰ C for crystallization, to obtain 2-isopropoxyphenyl - [[(diethoxyphosphinothioyl) anilino] thiojmethylcarbamat in the form of colorless crystals of mp 69 ° to 70.5 ° C.

The elementary analysis of the compound C ₂₁ H ₂ QN ₂ Ot is as follows:

Calculated: C 52.04 H 6.03 N 5.78 Found: C 52.03 H 6.18 N 5.78

Preparation of 2-isopropoxyphenyl- [(diethoxyphosphinothioyl) -n-propylamino] thio] methylcarbamate:

According to Example 2, Part B, but replacing the 0, O-diethyl-N- (chlorothio) phenylphosphoramidothioate with O, O-diethyl-N- (chlorothio) -n-propylphosphoramidothioate, the corresponding 2α-xsopropoxyphenyl-ε [( diethoxyphosphinothioyl) -n-propylamino thiojmethyl carbamate in the form of an amber oil.

The elementary analysis of the compound C ^ ßR-z * NpO ₁ -PSp gives the following values:

Calculated: C 4?, 98 H 6.94. N 6,22 found: C 47,47 Ή 6,90 N 6,26.

Preparation of Compound 3-Isopropylphenyl - {[(diethoxyphosphinothioyl) isopropyl] amino] thio-methylcarbamate:

According to Example 2, parts A and B, but with He set of 0,0-Diäthylphenylphosphoramidothioats and 2-Isopropoxyphenylmethylcarbamats by 0,0-Diäthylisopropylphosphoramidothioat bzv. 3 ™ Isopropylphenylmethylcarbamat. there is obtained 3-isopropylphenol ^ 1 ~ ^ [(diethoxyphos- phinothioyl) isopropylamino} thio} methyl carbamate in the form of an amber oil.

The elemental analysis of the compound CjgH ^ NpO / PS £ gives the following fourth:

Calculated: C 49.75 H 7,19 N 6,45 Found: C 49,43 H 7,09 N 6,39.

Example, 5

Preparation of methyl N- [[({[(dimethoxyphosphinothioyl) methylamino] thio} methylamino) carbonylJoxyjethanimidothioate:

Starting from the known compound Metnyl-N - {[(methylamino) carbonyl] oxyjäthanimidothioat and a suitable Phosphoramidothioats be obtained according to Example 2, Part B, the following new N - [(phosphinyl) amino thethi carbamate and N - [(phosphinothioyl) amino ] thiocarbamates:

Methyl-N - ^ [({[(dimethoxyphosphinothioyl) methylamino] thio} methylamino) carbonylJoxyj-äthanimidothioat, mp: 57 ° Ms 58 ⁰ C.

The elemental analysis of the compound CqELqN, S ^ O, P gives the following values:

Calculated: C 27.66 H 5.22 N 12.10 Found: C 27.88 H 5.27 N 11.95.

Methyl-N-1 [({[(dimethoxyphosphinothioyl) isopropylamino] thio} methylamino) carbonyl] oxy] äthanimidothioat, mp: 88 ° to 89 ⁰ C.

The elementary analysis of the connection CjqH ^ N-xO ^ PS ^ yields the following values:

Calculated: C 31.99 H 5.91 N 11.19 Found: C 31.99 H 5.86 N 10.93.

Methyl-N - {_ [({_ [(dimethoxyphosphinothioyl) -n-butylamino] -thio} methylamino) carbonyl] oxy] ethanimidothioate, m.p .: up to 61 ° C

The elemental analysis of the compound C ^ E ^ N ^ O ^ PS · gives the following values:

Calculated: C 33.92 H 6.21 N 10.79 found: C 33.84 H 6.26 N 10.44.

Methyl N - {[({C (diäthoxyphosphinothioyl) methylamino] thio} methylamino) carbonyl] oxy | äthanimidothioat.

The elemental analysis of the compound C ^ q ^h 2 2 ^ 3 ^o 4 ^PS 3 gives the following values:

Calculated: C 31.99 H 5.91 N 11.19 Found: C 32.00 H 5.96 N .10.58.

Methy1-Nf [({[(diethoxyphosphinothioyl) isopropylamino] thioj methylamino) carbonyl Joxyjethanethanimidothioate, mp: up to 73 ⁰ C.

The elemental analysis of the compound C ₁ gHgQN ^ O ^ PS yields the following values:

Calculated: C 35.71 H 6.50 N 10.41 found: C 35.77 H 6.74 N 10.09.

2107 94

Methyl-N- {[({[(diethoxyphosphinothioyl) -n-propylamino] -thio | methylamino) carbonyl] oxy ^ ethanimidothioate.

The elemental ^{analysis of} the compound ^ΰ ΐ2 ^Ή 28 ^Ν 3 ^Ο 4 ^ρ3 3 yields the following values:

Calculated: C 35.71 H 6.50 N 10.41 found: C, 35.48. H 6,46 N 9,82.

Methyl N - {[({[(diäthoxyphosphinothioyl) anilino] thio} me ~ methylamino) carbonyljoxy ^ äthanimidothioat, mp: 68 ° to 69 ⁰ C.

The elemental analysis of the compound CL, -Hp / N ^ CL PS ₇ , gives the following values:

Calculated: C 41.17 -H 5.53 N 9.60 found: C 40.80 H 5.43 N 9.37.

Methyl-N- {[({[(diethoxyphosphinyl) methylamino] thio] methylamino) carbonyl Joxyjethanimido thioate.

The elementary analysis of the compound C ^ HppN ^ O ^ PSp yields the following values:

Calculated: C 33.42 H 6.17 N 11.69 Found: C 33.26 H 6.17 N 11.28.

Methyl-N-f [({[(methoxy (methylthio) -phosphinyl) -methyl-amino] -thio} -methyl-amino) carbonyl Joxyj-ethane dimethioate, amber oil.

The elemental analysis of the compound CqILqN-O-PS., Yields the following values:

- «* - 2 10794

Calculated: C, 27.66, H, 5.22, N, 12.09 found: C, 27.44, H, 5.50, N, 11.60.

Methyl-N-4 L '(i C (methoxy (phenyl) phosphinothioyl) isopropylamino] thio} methylamino) carbonyl] oxy} äthanimidothioat, mp: 103 ° to 105 ⁰ C.

The elemental analysis of the compound CL cHp ^ N ^ O. PSp returns the following values:

Calculated: C 42.74 H 5.74 N 9.97 Found: C 42.62 H 5.67 N 10.02.

Methyl N - [({C (methoxy- (phenyl) phosphinothioyl-ethylamino-thio-methylamino) carbonyl] oxy-diethimidothioate, m.p .: 109 ° to 110 ° C.

The elementary analysis of the connection CL ^ HoqInUS ^ O ^ P yields the following values:

Calculated: C'39.68 H 5.12 N 10.68 Found: C, 39.73, H, 5.32, N, 10.92.

) Of methyl N- {[({[(methoxy (methyl) phosphinothioyl) methylaiüino] thio} methylamino) carbonyl] oxy} äthanimidothioat, mp: 87 ° to 88 ⁰ C.

The elemental analysis of the compound CqH ₁₈ N ^ 0 ^ S, P gives the following values:

Calculated: C 28.99 H 5.47 N 12.68 Found: C-29.61 H 6.00 N 12.84.

Methyl-N- {[(£ [(isopropoxy (phenyl) phosphinothioyl) Jthiolmethylamino isopropylamino) carbonyl] oxy | äthanimidothioat, mp: 100 ° to 102 ⁰ C.

The elemental analysis of the compound C ^ ILjqN ^ CUS ^ P yields the following values:

calculated: C 45.42. H 6.28 N 9.34 found: C 45.00. H 6,54 N 9,32.

Methyl-N- £ [({[(methyl (phenoxy) phosphinothioyl) methylamino] thiojmethylamino) carbonyljoxyj äthanimidothioat, mp: 65 ° to 67 ⁰ C.

Elemental analysis of Compound C, Hp ₀ N ^ 0-, PS, gives the following values:

Calculated: C 39.68 H 5.12 N 10.68 found: C 39.74 H 5.30 N 10.79.

Methyl-N- £ [({[(isopropoxy (methyl) phosphinothioyl) isopropylamino] thio} methylamino) carbonyl] oxy £ äthanimidothioat, mp: 90 ° to 92 ⁰ C.

The elemental analysis of the compound Cj p ^H 26 ^ 3 ^ 3 ^PS 3 ^ Sik * has the following values:

Calculated: C 37.19 H 6.76 N 10.84 found: C 37.39 H 7.0β Ν 10.72.

Methyl N - {[({[(methoxy (methyl) phosphinothioyl) isopropylamino] thio | methylamino) carbonylJoxyJäthanimidothioat, mp: 91 ° to 93 ⁰ C.

The elementary analysis of the compound C ^ qELoN-zO ^ PS ^ yields the following values:

Calculated: C 33.41 H 6.17 N- 11.69 Found: C 33.42 H 6.43 N 11.90.

Methyl N - {[({L '(methyl (phenoxy) phosphinothioyl) isopropylamino] thio $ methylamino) carbonyljoxyjäthanimidothioat, mp: 70 ° to 72 ⁰ C.

The elementary analysis of the compound C ^ Hp /, NVO-, PS · ^ gives the following values:

Calculated: C 42.74 H 5.74 N 9.97 Found: C 42.99 H 5.98 N 9.93.

Methyl-Nf [({[(ethyl (phenoxy) phosphinothioyl) anilino] thio} methylaniino) carbonyl] oxy} äthanimidothioat, mp: 74 to 76 ⁰ C.

The elemental analysis of the compound Cj qEL λN ^ CUPS- gives the following values:

Calculated: C 48.60 H 5.14 N 8.95 found: C 48.74 H 4.98 N 9.03.

Methyl-Νί- {[({[(4-chlorophenoxy (ethyl) phosphinothioyl) isopropylamino] thio} methylamino) carbonyl] oxy} -äthanimido- thioate, mp: 65 ° to 66 ⁰ C.

The elemental analysis of the compound C ^ HpcClN- ^ O ^ S ^ P gives the following values:

Calculated C 40.89 H 5.36 N 8.94 Cl 7.54 Found C 41.08 H 5.48 N 9.14 Cl 7.62.

Methyl-N-4 [({[(methyl (isopropoxy) phosphinothioyl) anilino] thio] methylamino) carbonyl] oxy} äthanimidothioat, mp: 76 ° to 78 ⁰ C.

The elemental analysis of the compound C ^ κΗ ^ λN ^ O ^ PS ^ gives the following values:

Calculated: C 42.73 H 5.74 N 9.97 Found: C 42.68 H 5.92 N 10.02.

Methyl-N - {[({[((L '" ¹ , 1'-biphenyl] -4-yloxy} ethylphosphinothioyl) isopropylamino] thio / methylamino) carbonyl] oxy | - ethanimidotliioate, as a pale yellow oil.

The elementary analysis of the connection CppH-zQM-zÖ ^ PS ^ yields the following values:

Calculated: C 51.64 H 5.91 N 8.21 Found: C 52.00 H 6.10 N 8.04.

Methyl-N- £ [({[(phenyl (phenoxy) phosphinothioyl) ethylamino] thio} methylamino) carbonyl] oxy} äthanimidothioat as white crystals, mp 122 ° to 123 ⁰ C.

The elementary analysis of the compound C ₁ yH ₂ / _f N ^ 0, PS ^ gives the following values:

Calculated: C 48.60 H-5.15 N 8.95 found: C 48.56 H 5.23 N 9.04.

2107

Methyl-N - {[(C (ethyl (phenoxy) phosphinothioyl) benzylamino] thiojmethylamino) carbonyl] oxyjäthanimidothioat as pale yellow 01.

The elementary analysis of the connection CpgHpgN ^ O ^ PS ^ gives the following values:

Calculated: C 49.67 H 5.42 N 8.69 Found: C 49.64 H 7.19 N 8.41.

Methyl-N - f [({[(ethyl (phenoxy) phosphinothioyl) -4-chloroanilino] thio} methylamino) carbonyl] oxy} ethanimidothioate as white crystals, mp 69 ° to 71 ⁰ C.

The elemental analysis of the compound C ^ gB ^ ClN ^ n PS ₃ er_ gives the following values:

Calculated: C 45.28 H 4.60 N 8.34 Found: C 47.62 H 5.12 N 8.00.

Methyl N - {[ ((- C (ethoxy (phenyl) phosphinethioyl) benzylamino] thio} methylamino) carbonyl Joxyjethanimidothioate as a Yellow Viscous Oil.

The elementary analysis of the connection CpgHpgN ^ O ^ PS- ^ yields the following values:

Calculated C 49.67 H 5.42 N 8.69 Found C 46.43 H 5.07 N 7.80.

Methyl-N-iC ({[(ethyl (phenoxy) phosphinothioyl) -n-butylamino] thiofmethylamino) carbonyl] oxy} ethanimidothioate as a yellow oil.

The elemental analysis of the compound C ₁₇ HpQN ₃ O ^ PS yields the following values:

Calculated: C 45.42 H 6.28 N 9.35 Found: C 45.46 H 6.42 N 8.62.

Methyl N - {[({[(2-chlorophenoxy (ethyl) phosphinothioyl) anilino} thio} methylamino) carbonyl} oxyimidothioate as a yellow oil.

The elemental analysis of the compound C ^ qHp ^ ClN ^ O ^ PS ^ gives the following values:

Calculated: C 45.28 H 4.60 N 8.34 Cl 7.03 Found: C 45.81 H 4.74 N 8.38 Cl 7.44.

Methyl N - {[({[(4-chlorophenoxy (ethyl) phosphinothioyl) anilinojthio] methylamino) carbonyl] oxy | äthanimidothioat in the form of white crystals, mp 60 ° to 62 ⁰ C.

The elemental analysis of the compound CjgHp ^ ClN ^ O ^ PS yields the following values:

Calculated: C 45.28 H 4.60 N 8.34 Cl 7.03 Found: C 46.25 H 4.92 N 7.87 Cl 6.88.

Methyl-N f [(f [(ethyl (phenoxy) phosphinothioyl) cyclohexylaminojthio | methylamino) carbonyljoxyfäthanimidothioat in the form of white crystals, mp 129 ° to 13O ⁰ C.

The elemental analysis of the compound C ^ qH ^ qN ^ O ^ PS ^ yields the following values:

-SLb-

0794

Calculated: C 47.98 H 6.36 N 8.83 Found: C 48.14 H 6.57 N 8.94.

Methyl-N- [[(([(ethyl (phenoxy) phosphinothioyl) -p-nitroanilino-thio-methylamino) carbonyl] oxy) ethanimidothioate.

Methyl-N- [[ { [(ethyl (phenoxy) phosphinothioyl) -o-methylanilino-thio-methylamino) carbonyl-oxy } ethanimidothioate.

Methyl-N-f [(| {(ethyl (phenoxy) phosphinothioyl) -m-trifluoromethylanilino} thio} methylamino) carbonyl] oxy | ethane imidothioate.

Methyl-N-f [({C (ethyl (phenoxy) phosphinothioyl) -o-chloroanilino} thio} -methylamino) -carbonyljoxy-tetanimidothioate.

Methy1-N - ^ [ ({[ (cyclohexyloxy (ethyl) phosphinothioyl) cyclohexylamino] thio (methylamino) carbonyl} oxyimidothioate.

Methyl-N- [[({[(ethyl (p-nitrophenoxy) phosphinothioyl) -anilino} thio} methylamino) carbonyljoxy / ethanimidothioate

Methyl-N - {[({[(ethoxy (phenyl) phosphinothioyl) anilino} thio} methylamino) carbonyl] oxyimidothioate.

Starting from suitable O - [(methylamino) carbonyl] oximes of 2-alkyl-1,3-dithiolane-2-carboxaldehydes and suitable phosphoramidothioates, the following compounds are obtained according to Example 2, Part B:

2-methyl-1,3-dithiolane-2-carboxaldehyde, 0- {{ (diethoxyphosphinothiyl) anilino} thio { methylcarbamoyl) oxime. 2-methyl-1,3-dithiolane ~ 2-carboxaldehyde, 0 - ({[(diethoxyphosphinothioyl) methylamino} thio} methylcarbamoyl) oxime.

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2-methyl-1-dithian-Z-carboxaldehyde, 0 - ({[(phenoxy (phenyl) phosphinothioyl) ethyl-amino] thio-methylcarbamoyl) oxime. 2-methyl-1-dithian-carboxaldehyde, 0 - ({[(diathoxyphosphinothioyl) anilino] thio} methylcarbamoyl) oxime. 2-ethyl-1,3-dithiane-2-carboxaldehyde, 0 - ({[(diethoxyphosphinothioyl) anilino} thio} methylcarbamoyl) oxime. 2-ethyl-1, S-dithiane-carboxaldehyde, 0 - ({[(ethoxy (phenoxy) phosphinothioyl) methylamino] thiojmethylcarbamoyl) oxime.

2-Me. Ethyl-1,3-dithiane-2-carboxaldehyde; 0- (f [(ethoxy (thiophenoxy) phosphinothioyl) methylamino] thio ^ methylcarbamoyl) oxime;

2-methyl-1,3-dithiane-2-carboxaldehyde, 0 - ({f (diethoxyphosphinoyl) anilino] thio} methylcarbamoyl) oxime.

Example 7

Starting from the known compound OrC (methylamino) -carbonyl] oxime of 1,3-dithiolan-2-one and suitable phosphoramidothioates, the following compounds are obtained according to Example 2, Part B:

1,3-dithiolane-2-one, 0 - ({[(Diäthoxyphosphinothioyl) methylaminoJthio \ methylcarbamoyl) oxime.

1,3-dithiolan-2-one, 0 - ({[(diethoxyphosphinyl) ethylamino] thio] methylcarbamoyl) oxime.

1,3-Dithiolan-2-one, 0 - ({[(diethoxyphosphinothioyl) anilino] thio] methylcarbamoyl) oxime.

1,3-dithiolan-2-one, 0 - ({[(phenoxy (phenyl) phosphinothioyl) methylamino] thio} methylcarbamoyl) oxime and 1,3-dithiolan-2-one, 0- {{ (phenoxy (phenyl) phosphinothioyl) ethylamino-thio} methylcarbamoyl) oxime.

Beis piel 8

Starting from the known compound of 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethyl.carbamate and suitable phosphoramidothioates, the following compounds are obtained according to Example 2, Part B:

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl - $ [(diethoxyphosphinothioyl) methylamino] thio | methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-f [(ethyl) (phenoxy) phosphinothioyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-ε- [(diethoxyphosphinothioyl) ethylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[(diethylphosphinothioyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl {[(ethoxy (phenyl) phosphinothioyl) anilino] thio} methylcarbamate, 2,3-dihydro-2 , 2-dimethyl-7-benzofuranyl-f [(ethoxy (ethyl) phosphinothioyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[(ethyl (thiophenoxy) phosphinothioyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl { [(p-chlorophenyl (methyl) phosphinothioyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2- dimethyl-7-benzofuranyl - {[(diethoxyphosphinyl) methylamino] thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- i [ (ethyl (p henoxy) phosphinyl) methylamino-thio} methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[(phenoxy (phenyl) phosphinyl) meth3''lamino] thio} methylcarbamate, 2,3 ~ I> ihydro- 2,2-dimethyl-7-benzofuranyl - / [(ethoxy- (ethyl) phosphinyl) anilino] thio-methylcarbamate and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl - {[(methyl (thiophenoxy) phosphinyl] ) anilino] thio} methylcarbamate.

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Example 9

Methyl-N - $ _ [. ({[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino) thio] ethylamino) carbonyl] -oxyjethane imidothioate:

A solution of 3.00 g (13.4 mmol) of 5,5-dimethyl-2-isopropylamino-2-thioxo-1,3,2-dioxaphosphorinane and 1.9 ml (13.5 mmol) of triethylamine in 2 ml Tetrahydrofuran is added dropwise within 20 min in a stirred solution of 1.00 ml (15.7 mmol) of sulfur dichloride in 20 ml of tetrahydrofuran at room temperature. After completion of the addition, the reaction mixture is stirred for 1 h at room temperature. Now, the mixture with 0.25 g of copper (I) chloride and then dropwise with a solution of 2.17 g (13.4 mmol) of methyl N - {[(methylamino) carbonyl] oxy} ethanimidothioaf and 1.90 ml (13.5 mmol) of triethylamine in 20 ml of tetrahydrofuran. After 2 hours of stirring at room temperature, the mixture is diluted with water and extracted with ethyl acetate. The separated organic phase is washed with water, dried over magnesium sulfate and then concentrated under reduced pressure. The resulting oily evaporation residue is chromatographed on silica gel using as eluent a mixture of ethyl acetate and Skellysolve B in the ratio 2: 3. The chromatographed product is recrystallized from ethyl acetate, whereby methyl N - {[({[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino) thio} methylamino) carbonylJoxyjäthanimidothioat in the form of a white solid, mp 114 ° to 115 ⁰ C is obtained. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elementary analysis of the compound C ^ HpgN-, 0, PS- yields the following values:

C 37.58 H 6,31 N 10,11 Found: C 37,63 H 6,25 N 10,11.

Methyl-N-f [({{(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) tert-butylamino] thio} methylamino) carbonyl] -oxyjäthanimidothioat:

A solution of 7.4 g (31 mmoles) of 2-tert-butylamino-5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane and 4.4 ml (31 mmoles) of triethylamine in 50 ml of tetrahydrofuran added dropwise within 20 min with stirring in a cooled to a temperature of ^{0 0} C solution of 2.0 ml (31 mmol) sulfur dichloride in 20 ml of tetrahydrofuran. When the addition is complete, the mixture is stirred for a while at a temperature of ⁰ ° C., whereupon the mixture is treated with 0.3 g of copper (I) chloride and then dropwise over 20 minutes with a solution of 5.1 g (31 mmol). Methyl-N- [(methylamino) carbonyl] oxyjäthanimidothioat and 4.4 ml (31 mmol) of triethylamine in 50 ml of tetrahydrofuran is added. Upon complete addition, the mixture is stirred for 2 hours, allowing to warm to room temperature. Thereafter, the mixture is diluted with ethyl acetate and washed with ^{1 of} water. The separated organic solution is dried over magnesium sulfate and concentrated under reduced pressure. The resulting evaporation residue is treated with a 1: 2 mixture of ether and hexane to precipitate a crude product. After two changes

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crystallize from methanol to obtain an analytically pure material of a Fp of 167 ° to 168.5 ⁰ C. The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

The elementary analysis of the compound C ^ 4.H ₂₈ N ^ Or PS ^ gives the following values:

Calculated: C 39.14 H 6.57 N 9.78 found: C 39.45 H 6.73 N 9.87.

Example 11

Methyl N - {[(i [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio] methylamino) carbonyl] -oxyjäthanimidothioat:

A solution of 12.4 g of 2-cyclohexylamino-5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran is stirred with within 15 min in a to a temperature from -5 ° to ^{0 0} C cooled solution of 3.0 ml of sulfur dichloride in 50 ml of tetrahydrofuran registered. When the addition is complete, the mixture is stirred for 45 minutes at a temperature of ⁰ ° C. and then mixed with 0.20 g of copper (I) chloride and finally within 15 minutes with a solution of 7.67 g of methyl N- [ (methylamino) carbonyl] oxy? added ethanimidothioate and 6.55 ml of triethylamine in 50 ml of tetrahydrofuran. When the addition is complete, the mixture is stirred, allowing to warm to room temperature over 75 minutes, then the mixture is diluted with water and extracted with ethyl acetate.

dried and concentrated under reduced pressure

Recrystallization of the semi-solid residue from ethyl acetate / hexane gives 9.36 g of methyl Nf C (i [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio} methylamino ) carbonyl] oxy} äthanimidothioat in the form of a white solid, mp 133 ° to 14O ⁰ C.

The elementary analysis of the compound C ^ gE ^ N ^ O ^ PS ^ gives the following values:

Calculated: C 42.18 H 6.64 W 9.22 Found: C 42.39 H 6.71 N 9.32.

The nuclear magnetic resonance spectrum and the IR spectrum correspond to the expected structure.

Methyl ~ N ~ £ [({[isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio-methylamino) carbonyl] oxyjethaneimidothioate:

A solution of 10.94 g of 5,5-diethyl-2-isopropylamino-2-thioxo-1,3,2-phosphorinane and 6,05 ml of triethylamine in 50 ml of tetrahydrofuran is added dropwise within 15 min in a to a temperature of -5 ° to 0 C cooled solution of 2.72 ml of sulfur dichloride in 50 ml of tetrahydrofuran. After completion of the addition, the mixture is stirred for 1 h at a temperature of 0 ⁰ C, then 0.10 g of copper (I) chloride and then dropwise over 15 min, a solution of 7.06 g MethyI-N - {[(( methylamino) carbonylJoxyjäthanimidothioat and 6.05 ml

Triethylamine in 50 ml of tetrahydrofuran are added. Thereafter, the mixture is stirred and allowed to warm to room temperature over 1 h. Now it is diluted with water and extracted with ethyl acetate. The extracts obtained are washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The resulting oily evaporation residue is chromatographed on silica gel using a 1: 1 mixture of ethyl acetate and hexane to elute. Recrystallization from ethyl acetate / hexane gives methyl N - {[("" [isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino] thio} methylamino) carbonyl ] oxy} -äthanimidothioat in the form of a white solid having a melting point of 123 ° to 124.5 ⁰ C.

The elementary analysis of the compound CL c-ILqN ^ O, PS ^ gives the following values:

Calculated: C 40.61 H 6.82 N 9.48 Found: C 40.83 H 6.91 N 9.60.

The nuclear magnetic resonance spectrum and IR spectrum correspond to the expected structure.

Example 13

Starting from suitable methyl carbamates and phosphoramidothioates according to Example 10, the following compounds are obtained:

Methyl N - {[(f isopropyl (2-thioxo-1,3,2-phospholan-2-yl) -amino-thio} methylamine) carbonyl] oxy | ethaneimidothioate, mp: 120 ° to 122 ° C.

The elemental analysis of the compound C ^ qELqN-O »PS- yields the following values:

Calculated: C 32.16 H 5.40 N 11.25 Found: C 32.17 H 5.31 N 11.49.

Methyl £ [({[cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio ^ methylamine) carbonylJoxyjäthanimidothioat, mp: 155 ° to 157 ⁰ C.

The elemental analysis of the compound C ^ gH-, λ N ₇ .O ^ PS gives the following values:

Calculated: C 44.70 H 7.09 N 8.69 Found: C 44.96 H 7.11 N 8.81.

Methyl - {[({[isopropyl (2 ~ thioxo-1,3,2-dioxaphosphorinane-2-yl ·) amino] thio} me methylamino) carbonyl] oxy} äthanimidothioat, mp: 153 ° Ms 154 ⁰ C.

The elementary analysis of the compound C ^^ HpoN-zO ^ PS ^ yields the following values:

Calculated: C 43.10 H 5.72 N 10.84 Found: C 34.21 H 5.87 N 11.13.

Methyl {[ ([ethyl] (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thiopmethylamino) carbonyl] oxy) ethanimidothioate, m.p .: 111 ° to 112 ° C.

The elemental analysis of the compound C ^ pHpA ^ OrPS gives the following values:

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calculated: C 35 90 H 6 03 N 10 , 47 found: C 36 13 H 6 22 N 10 , 26th

Methyl-Ni [({[isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino} thio} methylamino) carbonylJ oxyläthanimidothioat, mp: 123 ° to 127 ⁰ C.

The elemental analysis of the compound C ^ H ^ yN- ^ O ^ PS yields the following values:

Calculated: C 39.24 H 6.35 N 9.80 found: C 39.76 H 6, $ 4 N 9.76.

Methyl-N - {[(ε [(2-thioxo-4H-1,3,2-benzodioxaphosphorin-2-yl) isopropylamino-thio-methylamino) carbonyl-oxy} ethanimidothioate,

Methyl-N- £ [(f [(2-thioxo-1,3,2-dioxaphospholan-2-yl) -methylamino-thioj-methylamino) -carbonyl-jxyjethane-imidothioate, methyl N - {[({[ethyl] (hexahydro-2-oxo-1 , 3,2-benzodioxaphospholan-2-yl) aminoJthio} methylamino) carbonyl] oxy | äthanimidothioat,

Methyl-N - {[ ( isopropyl (2-oxo-1,3,2-benzodioxaphospholan-2-yl) aminoethylthio] methylamino) carbonyl] oxyfethanimidothioate, methyl-Ni [({[benzyl (5,5-diethyl) 2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino-1-thio} methylamino) carbonyl-joxy-ethanimidothioate and

Methyl-N- [[(f [methyl (2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino Jthio} methylamino) carbonylJoxy} äthanimidothioat, mp: 94 ° to 96 ⁰ C.

The compounds of the formulas I, I ^! "I" and I " ¹ are effective pesticides for the control of non-harmful pests in agriculture, industry and in the home.

"Compounds" were compared to the starting methyl carbamates.

Representative pest species from the order "Lepidoptera", in particular the Southern Army Worm (SAW) (Prodenia eridania Cramer), the Tobacco Budworm (TBW) (Jieliothis virescens) and the Kohlspanner (CL) (Trichoplusia ni), from the order "Acarina in particular the double spotted spider mite (TSSM) (Tetranychus urticae Koch), from the order "Diptera" in particular the house fly (HF) (Musca domestica Linnaeus) or the yellow fever mosquito (YFM) (Aedes aegypti), from the order "Orthoptera" in particular the Cretaceous (HC) (Acheta domesticus Linnaeus) or the German Cockroach (GC) (Blatella germanica Linnaeus) or from the order "Coleoptera" in particular the cotton boll beetle (BW) (Anthonomus grandis Boheman) used.

The effectiveness against invertebrate pests could already be determined at concentrations of 0.5 ppm, depending on the type of pest. Some invertebrate pests are more sensitive to the compounds of the invention than others, others may be very resistant. In general, the compounds of the formula I are used in concentrations of about 30 to about 6000 ppm.

In general, the compounds of the invention show a mortality activity corresponding to the starting methylcarnate, but at the same time they are less toxic and phytotoxic. Mammalian toxicity is partially indicated.

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4- (Dimethylamino) -3,5-xylyl {[(diethoxyphosphinothioyl) n-propylamino] thio] methylcarboxylate:

Insect dose mortality

SAW 100 ppm 100

YM 0.6 ppm 100

Methyl-N - ^ [({[(diäthoxyphosphinothioyl) isopropylamino] thio ^ methylamino) carbonyl] oxy | äthanimidothioat:

insect

SAW CL BW HF YFM

Methyl-N - ^ [({[(methoxy (phenyl) phosphinothioyl) isopropylamino] thio ^ methylamino) carbonyljoxyjethanimidothioate:

Insect amount. mortality

SAW 3.3 ppm 90

CL 3.3 ppm 50

HP 25 ppm 50

BW 25 ppm 80

Methyl-N-f {(f [cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio | methylamino) carbonyl] -oxyjäthanimidothioat:

amount mortality 3.3 ppm 100 3.3 ppm 100 50 ppm 60 25 ppm 80 1.0 ppm 100

1 07

Insect amount mortality

SAW 11 ppm 70

CL 11 ppm x 87.5

THi 11 ppm 95

Mammalian toxicity - oral. LD ₁ -Q (rats) > 8000 mg / kg

Methyl N - {[(isopropyl (5,5-diethyl-2-thioxo ~ 1,3,2-dioxaphosphoran-2-yl) amino} thio} methylamino) carbonyljoxy} -ethanimidothioate:

Insect amount mortality

SAW 11 ppm 60

CL 11 ppm 95

TB 11 ppm × 100

Mammalian toxicity - oral LD ^ ₀ (rats)> 2000 mg / kg

Methyl N - {[({[isopropyl (2-thioxo ~ 1,3,2-phospholane-2 ~ yl) ~ amino jthio} · me methylamino) carbonyl joxyj äthanimido thioate, 1 ^: 120 ° to 122 ⁰ C;

Insect amount mortality

SAW 11 ppm 40

CL 11 ppm. 48

TB 11 ppm 45

Methyl Nf [( { [cyclohexyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino] thio-methylamino) carbonyl] oxy} ethanimidothioate, mp: 155 ° to 157 ° C:

Insect amount mortality

SAW. 11 ppm 70

CL - 1Ί ppm 77.5

TB 11 ppm 95

Mammalian toxicity - oral LD ™ (rats) ^> 8000 mg / kg

Methyl N - {[({[isopropyl (2 - thioxo-1,3,2-dioxaphosphorinane-2-yl) amino] thio ^ methylamine) carbonyljoxy ^ äthanimidothioat, mp: 153 ° to 154 ⁰ C:

Insect amount mortality

SAW 11 ppm 56

CL 11 ppm

TB 11 ppm

Mammalian toxicity - oral LD ₁ -Q (rats)> 2000 mg / kg

Methyl-Nf [(ί [ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino] thiο} methylamino) -carbonyl-joxy} -ethanimidothioate, m.p .: 111 ° to 112 ° C :

Insect amount mortality

CL 11 ppm 56

Methyl N - {[(isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino] thio (ethylamino) carbonyl] oxy} ethanimidothioate, mp: 123 ° to 127 ° C:

Insect amount mortality

CL 11 ppm 92.5

The details of the mortality test are as follows:

Preparation of the tested chemicals: Analytically pure samples of the various compounds are dissolved in acetone. These acetonic solutions are applied as such or in a diluted with a Tween 20 "dampening" or with a 10% cane sugar "dampening" diluted form. As such, "fountain solution" as such contained 0.132% (v / v) Tween 20 (polyoxyethylene sorbitan monolaurate).

Southern armyworm and cabbage strain tests were performed on leaves of Henderson lima bean. This bush bean has two primary leaves per seedling. The leaves were immersed in an emulsion of the compound to be tested in the "moistening water" and allowed to dry. Then they were placed on a moistened filter disc in a 9 cm diameter plastic Petri dish. Five larvae of each insect to be tested were placed on the leaves, after which the lid of the Petri dishes was removed and the Petri dish was set aside for further evaluation. For each treatment dosage, three parallel experiments were performed.

The crickets test was performed by pipetting 5 ml portions of the acetone solution into 9 cm diameter Petri dishes. Then the acetone was smoked off. 10 dummy dolls were now placed in each treated petri dish, after which the lid was replaced. For each treatment dosage, three parallel experiments were performed.

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The house fly and cotton bollard beetle tests were conducted by saturating a 10 ml golf ball sized cotton ball of a preparation of the test compound prepared using a 10% cane sugar containing "dampening" water , The saturated jar was then placed in a portioning bowl attached to the inner wall surface of a waxed paper cup. The paper cup had a capacity of 141.7 g. 10 adult house flies or 10 boll weevils were placed in the waxed paper cups, whereupon they were covered with a plastic lid for further observation. For each treatment dosage, two parallel experiments were performed.

The larvae of the yellow fever mosquitoes were tested by adding 100 ml of distilled water with appropriate amounts of a solution of the compound to be tested in the "fountain solution" or the acetone solution. The water was in a waxed paper cup with a capacity of 141.7 g. Now 10 yellow fever mosquito larvae were placed in the paper cups and 24 hours later dried yeast was added. For each treatment dosage two comparative experiments were performed.

The tests, which were carried out using the southern armyworm, of the cricket, the boll weevil, the house fly and of the carbon tensioner, were incubated at 22 ⁰ C, the tests were carried out using the yellow fever mosquito larvae were allowed to proceed at a temperature of 27 ⁰ C calmly.

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Tease tests were evaluated after 24, 48 and 72 h, respectively. Died insects also included dying insects or insects left on the ground.

In further experiments phytotoxicity, residual activity and mammalian toxicity were tested, for example. Methyl-N-4 [({[(diethoxyphosphinothioyl) isopropylamino] thio [methylamino] carbonyl] oxyimidethioate was compared with the starting compound methyl-N-ε [(methylamine)) carbonyl] oxy} ethanimidothioate. It was based on a scale where 0 indicates no damage and 10 indicates complete plant death. The novel compounds according to the invention are generally less phytotoxic than the parent compound and significantly less phytotoxic to sensitive plants, for example the eggplant plant. Typically, the compounds of the invention have an average phytotoxicity index in the range of about 1.0 to 1.5 at a concentration of 300 to 600 ppm after an exposure time of 8 days. The parent compound has corresponding index values of 4.25 to 5.0.

The compounds of the invention were further tested for their residual activity (on the leaves) against Southern armyworm larvae on lima bean seedlings. The compound of the invention methyl-N- {Γ (ζ [(diethoxyphosphinothioyl) isopropylamino] thio ^ methylamino) carbonyl] oxyjäthanimidothioat still gives a 100! & Lge mortality 7 weeks after the implementation of the treatment. Activity of mother compound in equivalent quantity decreased already after 14 days to 20/6.

- W3 -

When compared to the oral toxicity carried out on male rats, the compound according to the invention has methyl-N- {[(C 1 -C (diethylphosphinothioyl) -isopropylamino] thio [methylamino) carbonyl] oxy. Ethanimiclothioat proved to be less than a quarter as toxic as the methyl carbamate parent compound. The oral LDc ₀ values are 105 mg / kg body weight or 17 to 24 mg / kg body weight.

As already stated, the compounds of the formula Ia are particularly effective. Thus, for example, the compound MethyI-N- {[(- {[(ethyl (phenoxy) phosphino thioyl) anilino] thio | methylamino) carbonyl] oxy | ethanimidothioate has up to 3 times the insecticidal activity of the parent compound methyl-N - {[ (methylamino) carbonyl] oxyjäthanimidothioat (Methomyl) against Lepidopterusarten, for example the southern armyworm (SAW) and the Kohlspanner.

The described tests show that the compounds according to the invention are able to solve the stated problems and make a significant contribution in the field of pesticides. They further show that the inventive N - [(phosphinyl) amino] thio and N - [(phosphinothioyl) amino] thiomethylcarbamate for controlling noxious insects in the form of the pure compound, as prepared according to the examples, in the form of technically pure compounds the large-scale production or in the form of mixtures of special compounds can be used. On the other hand, for practical reasons, it may be convenient for those skilled in the pesticides field to use diluent vehicles and, if appropriate, other adjuncts containing the distribution of the active compounds to combat pests and

to increase effectiveness and 'promote profitability, to hand.

There are a large number of diluents or carrier materials which are suitable for use in the field of pest control and for the preparation of pesticidal compositions using the compounds according to the invention. Typically, dispersible carrier materials are used. Such carrier materials may contain other adjuvants, e.g. Wetting agents, emulsifying agents, adhesion improving agents and other components which indirectly contribute to an improvement in the effect.

The novel carbamates according to the invention of the formulas I, I ¹ , I "and I" ^! can be used against insects, roundworms (nematodes) and mites. They can be used in the form of pesticidal agents, for example dusts, wettable powders, emulsifiable concentrates, aqueous dispersions, solutions and flowable creams. The agents in question can be applied to any location, eg on the ground, on plants, on leaves, on seeds or on other plant parts.

Granular agents may be applied to the soil or to surfaces after their preparation. Furthermore, the compounds of the formulas I, I ¹ , I "and I" ^! may be the only active ingredient in a pesticidal agent, or the particular pesticidal agent may contain other agents having insecticidal, miticidal or nematocidal activity.

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Those compounds of the formulas I, I ¹ , I "and I ¹ " according to the invention which are solid can easily be processed into dusts by milling together a mixture of the relevant compound (s) and a pulverulent carrier material. This milling is usually carried out using a ball mill, a hammer mill or by Luftgebläsezerstäubung.

Conveniently, the particle size of the individual particles is less than 60 microns. Preferably, 95% of the particles have a particle size of less than 50 microns, about 75% of the particles have a particle size of 5 to 20 microns. Dusts of the mentioned fineness, comminution or distribution are usually free-flowing powders. They may be applied to animals, to inanimate objects, fruit trees, crops and soil so as to obtain a suitable distribution or coverage. The dusts are particularly suitable for controlling insects and mites, by dusting the pesticides concerned with airplanes. Dusts are also suitable for application to the underside of foliage.

Typical examples of suitable powdery carrier materials are natural clays, e.g. Chinaton, Georgia clay, bard clay, attapulgite, kaolin and bentonite clay. Minerals can be used in their natural form as extracted from the soil. Examples of these are talc, pyrophillite, quartz, diatomaceous earth, Fuller's earth, chalk, sulfur, silica-containing materials such as silicic acid and silicates, and the like. Furthermore, the minerals in question can be chemically modified. Examples are washed

-Hk-

Bentonite or colloidal silica. Finally, organic substances in flour-like form, e.g. Wood, walnut shells, soybean meal, cottonseed meal, tobacco meal and free-flowing hydrophobic starches.

Dusts are also obtained by dissolving the "phosphinic acid derivatives of the aminothiomethylcarbamate pesticides of the formulas I, I ¹ , I" and I ¹ "in a volatile solvent, for example methylene chloride, mixing the resulting solution with a powdered carrier and then evaporating the solvent ,

The proportion of powdered carrier and active compound of the formula I, I ¹ , I "and I" ¹ can be very different depending on the intended use, the control of roundworms (nematodes) or mites and the treatment conditions. In general, dusts can be up to about 90 wt. ~ Contain ° / o of active ingredient.

Pesticidal compositions according to the invention in the form of dispersible powders are obtained by incorporating a surfactant in a dust-like agent prepared in the manner described above. When about 0.1 to about 12% surfactant is incorporated into a dusty agent, the resulting dispersible powder is particularly well suited for further mixing with water for spraying on inanimate objects and products, fruit trees, crops, soil and living Animals, eg Livestock. The dispersible powders may be mixed with water to produce any concentrations of active ingredient. The mixture can then be applied in such an amount that the desired amount of application and the

equal distribution achieved. In consideration of this versatility, the dispersible powders according to the invention may preferably contain from about 5 to about 80% of active ingredient.

Typical examples of pesticidal agents useful as dispersible powders according to the invention are alkyl sulfates and sulfonates, for example alkylaryl sulfonates, succinic acid esters, polyoxyethylene sulfates, polyoxyethylene sensorblatan monolaurate, alkylaryl polyether sulfates, alkylaryl polyether alcohols, alkylnaphthalenesulfonates, alkyl quaternary ammonium salts, sulfated fatty acids and their esters, sulfated fatty acid amides, glycerol mannitol laurate, polyalkyl ether condensates of fatty acids, lignin sulfonates, and the like. Preferred surfactants are mixtures of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77), mixtures of polyethoxyethanols (Tritone X-151, X-161, X-171), for example, about equal parts of sodium kerobenzene sulfonate and isooctylphenoxypolyethoxyethanol with about 12 ethoxy groups. and mixtures of calcium alkylarylsulfonates and polyethoxylated vegetable oils (Agrimul N ₂ S). Of course, the said sulfates and sulfonates are preferably used in the form of their soluble salts, for example their sodium salts. All of these surfactants are capable of lowering the surface tension of water in concentrations of about Λ% or less. Dispersible powders are also obtained, if necessary, using mixtures of surfactants of the said types.

A suitable disperseable powder is obtained, for example, by mixing and grinding 327 kg

Georgia clay, 4.5 kg isooctylphenoxypolyäthoxyäthanol (Triton X-IOO) as a wetting agent, 9 kg of a polymeric sodium salt of a substituted benzoid-long-chain sulfonic acid (Daxad 27) as a dispersant and 113 kg of the active ingredient, for example the compound of Example 2 The dispersible powder obtained has the following percentage composition (in parts by weight, unless stated otherwise):

Active Ingredient 25% isooctylphenoxypolyethoxyethanol Λ% polymeric sodium salt of a substituted benzoid long chain sulphonic acid 2% Georgia clay 72%.

Dispersing such a dispersible powder in an amount of 4.54 kg in 379 liters of water gives a sprayable agent having about 0.3% (3,000 ppm) of active ingredient which can be used against insects or mites on plants. Fruit trees or other whereabouts of the insects or mites can be applied or sprayed onto the ground to control nematodes.

Optionally, dispersants, e.g. Methyl cellulose, polyvinyl alcohol, sodium lignosulfonates and similar dispersible powders according to the invention. Furthermore, adhesive or sticky agents, e.g. Vegetable oils, naturally occurring gums, casein, Zonarez B, a series of polymerized terpenes, Unicez 709, a maleic acid based resin, polypoles, partially dimerized resin acids and Dymerex, a dimeric rosin acid, and the like. Furthermore, corrosion inhibitors, e.g. epichlorohydrin,

and anti-foaming agents, e.g. Stearic acid, added. Methods of incorporating these agents into pesticides are known to those skilled in the art.

The novel compounds of the formulas I, I ¹ , I "and I" ¹ according to the invention can be applied to insects, mites, objects or a situs also in the form of aqueous sprays without solid carrier. However, since the compounds per se are relatively water-insoluble, they are preferably dissolved in a suitable inert organic solvent carrier. Conveniently, the Lösüngsmittelträger should not be miscible with water, so that one can prepare an emulsion of the solvent carrier in water. For example, if a water miscible solvent carrier such as ethanol is used, the solvent carrier in solution in the water, wherein any excess of compound of formula I, I ¹ , I "or I" ¹ precipitates out of the solution. In an oil-in-water emulsion, the solvent phase is dispersed in the aqueous phase, the dispersed phase containing the active ingredient. In this way an even distribution of a water-insoluble active ingredient is achieved in an aqueous spray. A solvent carrier in which the novel compounds of the formulas I, I ^! "I" or I "'are highly soluble should suitably be such as to provide relatively high concentration pesticidal agents on the active ingredient. Sometimes, one or more solvent carriers, with or without cosolvent, can be used to prepare concentrated solutions of the active ingredient. The main consideration here, however, is to use a water-immiscible solvent for the active ingredient in order to make it the compound for a concentrate.

-SO-

solution, as required for application to insects and mites.

The emulsifiable concentrates according to the invention are thus obtained by dissolving the active ingredient and a wetting agent in a water-immiscible solvent carrier, for example a Lösungsinittelträger in V / asser at a temperature in the order of 20 ° to 30 ⁰ C in a Amount of less than 2.5 % , such as cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbons such as benzene, toluene or xylene, or a high boiling petroleum hydrocarbon such as kerosene, diesel oil and the like. Optionally, together with the solvent carrier to improve the solution of the active ingredient, a cosolvent, such as methyl-? ethyl ketone, acetone, isopropanol and the like. Aqueous emulsions are then obtained by mixing the respective solution with water to the desired concentration of active ingredient. The surfactants used in the aqueous emulsions according to the invention correspond to the already mentioned surfactants. Of course, if necessary, mixtures of surfactants can be used.

Conveniently, the concentration of active ingredient in the emulsifiable concentrates is from about 5 to about .50, preferably from about 10 to about 40 weight percent. A concentrate of 20 wt -.% Of the dissolved in a water-immiscible solvent of the type described compound having an aqueous medium in an amount of 13 ral concentrate to 3.79 1 Medium mixed v / ground,

to obtain a mixture containing 700 parts of active ingredient per million parts of liquid carrier. Similarly, 1.06 L of a 2O $ concentrate can be mixed with 155 L of water to produce a pesticidal agent at about 1200 ppm. on active ingredient. In the same way, more concentrated solutions of active ingredient can be prepared.

The pesticidal compositions of the present invention in concentrate form which are ultimately to be used in the form of aqueous dispersions or emulsions may contain humectants, i. Agents which delay the drying of the agent in contact with the material to which it is applied. Suitable humectants are, for example, glycerol, diethylene glycol, solubilized lignins, e.g. Calcium lignosulfonate, and the like.

Pesticidal compositions according to the invention in granular form are suitable for application to the soil, if a lasting effect is desired. Grains can be easily scattered by hand, over wide areas or localized, e.g. rows. The individual granules may have any size from 0.246 to 1.651, preferably from 0.351 to 0.833 mm. The granules are obtained by dissolving the active compound in a solvent such as methylene chloride, xylene or acetone and applying the solution to a certain amount of a granulated absorbent carrier. Examples of granulated adsorbed carriers are ground corncobs, ground walnut shells, ground peanut shells, and the like. Optionally, the impregnated, granulated absorbent carrier may be provided with a coating. This

Coating preserves the integrity of the grain until it is applied to an object or site suitable for release of the active ingredient.

The amounts of application to insects, mites, the soil or any other site depend on the type of harmful organism to be controlled, the presence or absence of beneficial organisms, the temperature conditions in the treatment and the method of application and the efficacy of the application. In general, insecticidal and miticidal activity is achieved when the compounds are applied in concentrations of about 5 to about 2,000 ppm, preferably from about 30 to about 1,000 ppm. E ¹ urine nematodes require 4.5 to 22.7 kg per 4050 m.

The pesticidal compositions according to the invention with the novel thiocarbamates of the formulas I, I ¹ , I "and I" ¹ can be applied by customary known methods to insects, mites, nematodes, the soil or any other site. Thus, for example, a floor surface, a building or plants can be treated by application of a wettable powder from a hand-operated backpack sprayer. If you want to treat livestock, you can work with dipping baths. Dusts can be applied by powder atomizers or by manually operated atomizing devices. Creams and ointments can be applied to the skin or objects for long-term protection against insects or mites.

The active compounds according to the invention can also be used for administration in the household to relatively dilute compositions in a dispersible insecticide carrier.

work. For example, a dust aerosol may contain about 0.1 to 5.0% active ingredient and otherwise deodorized kerosene.

Of course, a variety of variations may be required when using the compounds of the invention as pesticidal agents. This depends, for example, on pest insect infestation, the pest insect to be controlled in each case, the specific site to be treated, the plant species, the prevailing weather conditions, e.g. temperature, relative humidity, rain, dew, and the like.

Claims (20)

2107 94: ixfinding claim:> 1. An insect pest control agent which comprises, in addition to an excipient, a biologically effective amount of at least one N - [(phosphinyl) amino-thio-and / or N - [(phosphinothioyl) amino] thiomethylcarbamate of the general formula: in which mean: R is a radical of the formula:
a) in which Rp, R * and R-, which may be identical or different, each represent a hydrogen or halogen atom, a short-chain alkyl group having 1 to 5 carbon atoms inclusive atom (s), a short chain alkoxy group having 1 to 5 inclusive carbon atom (s), a short chain alkylthio group having 1 to 5 carbon atoms inclusive, a dialkylamino group whose alkyl parts are the same or different and have 1 to 3 inclusive carbon atom (s) may represent, or a radical of the formula -N = CHN (CH ₃ ) ₂ ;
b) BC = N- "
t wherein A and B, which may be the same or different, each having a copper-chain alkyl group having 1 to 5 carbon atoms inclusive, a short chain alkylthio group having 1 to 5 inclusive carbon atoms, a monocyano-substituted alkylthio group having T to 5 inclusive carbon atoms (s ), a phenylthio group whose phenyl portion is optionally substituted by 1 to 3 (same or different) substituents consisting of halogen atoms or short-chain alkyl groups of 1 to 4 carbon atoms inclusive, a cyano group, an alkoxy group of 1 to 5 inclusive carbon atom (s ), a phenyl radical or a hydrogen atom, it being understood that in the case where B is a hydrogen atom, A is of the formula: R ₆ -CSR ₅ R ₇
corresponds, in which mean: c. an alkyl group having 1 to 3 inclusive carbon atom (s) or a phenyl group; r is an alkyl group having 1 to 3 inclusive carbon atom (s); and an alkyl radical having 1 to 3 carbon atoms inclusive or a radical of the formula -SRq, in which Rq is an alkyl radical corresponding to the alkyl radical represented by R 1, or R (- and Rq together with the atoms to which they are attached, a heterocyclic ring containing two sulfur atoms of the formula: in which η = 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals (e); or A and B together with the carbon atom to which they are attached, a heterocyclic ring containing two sulfur atoms of the formula: wherein m = 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radical (s), or c) '. , PL is a short-chain alkyl radical, an optionally substituted phenyl radical, a phenyl-substituted short-chain alkyl radical or a Cyelοalkylrest; X represents an oxygen or sulfur atom and Z 1 to Z 3, which may be identical or different, each represent a hydrogen atom or a methyl or ethyl radical and k = 0 or 1, contains. 2. Composition according to item 1, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is a sulfur atom. 3. Composition according to item 1, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom. -> - 210794 4. Composition according to item "3, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom and R is an alkanimido radical of the formula B-C = N in which A is a hydrogen atom or a short-chain alkyl radical and B is a short-chain alkylthio radical. ~ 5 * 9 - in which A is a hydrogen atom or a short-chain alkyl radical and B is a short-chain alkylthio radical, and Zp, Z, - and Zr are short-chain alkyl radicals. , 5. Composition according to item 4, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom, R is an alkanimido radical of the formula B-C = N in which A represents a hydrogen atom or a short-chain alkyl radical and B represents a short-chain alkylthio radical, and Zc and Zc correspond to short-chain alkyl radicals. 6. Composition according to item 4, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom, R is an alkanimido radical of the formula B-C = N in which A is a hydrogen atom or a short-chain alkyl radical and B is a short-chain alkylthio radical and Z 1 to Z 7 are hydrogen atoms. ^ 7 ™ ϊ dioxaphosphorinan-2-yl) amino / thioymethylamino) carbonyl / fc * "* β / * v / oxy} -ethanimidothioate and / or Methyl-K- j I (1 [methyl (2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino-1-thio-methyl-amino) carbonyl-oxy-ethanimidothtate contains " 7. Composition according to item 4, characterized in that it contains at least one compound of the formula given in claim 1, v / orin X is an oxygen atom, R is an alkanimido radical of the formula B-C = N 8, agent according to point 5, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom, R is an alkanimido radical of the formula B-C = N in which A is a hydrogen atom or a short-chain alkyl radical and B is a short-chain alkylthio radical, Z ₁ - and Zr are short-chain alkyl radicals and R ^ is a short-chain alkyl radical. 9. Composition according to item 4, characterized in that it contains at least one compound of the formula given in claim 1, wherein X-stands for an oxygen atom, R is an alkanimido radical of the formula B-C = N in which A is a hydrogen atom or a short-chain alkyl radical and B is a short-chain alkylthio radical, Z ₁ to Zr are hydrogen atoms and R 1 is a short-chain alkyl radical. 10. Composition according to item 7, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom, R is an alkanimido radical of the formula B-C = N t A represents, in which A is a hydrogen atom or a is a short-chain alkyl radical and B is a short-chain alkylthio radical, Zp, Z _x - and Zr are short-chain alkyl radicals and R ^. represents a short-chain alkyl radical. 21 Q794 11. Composition according to item "5, characterized in that it contains at least one compound of the formula given in claim 1, wherein X is an oxygen atom, R is an alkanimido radical of the formula B-C = N A in which A represents a hydrogen atom or a short-chain alkyl radical and B represents a short-chain alkylthio radical, Z ₅ and Zg correspond to short-chain alkyl radicals and R ^ represents a cycloalkyl radical. 12. Composition according to item 8, characterized in that it is an active ingredient Methyl-N - {[({[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) isopropylamino} thio} methylamino) carbonyl Joxyj-ethaneimidothioate, Methyl-N-i [({[(5,5-dimethyl-2-thloxo-1,3,2-dioxaphosphorinan-2-yl) tert -butylamino] -thio-methylamino) carbonyl-JJ; 'Methyl-N-J {({[isopropyl (5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) -amino] -thio-methyl-amino) carbonyl, J-oxy-iodo-imidothioate and / or Methyl-N-J [({L-ethyl (5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino } thio } methylamino) carbonyl-Joxy) -ethanimidothioate
contains. 13. Composition according to item 9, characterized in that it is an active ingredient Methyl N- / [({L-isopropyl (2-thioxo-1, 3,2-phospholan-2-yl) amino} thio (methylamino) carbonyl-Joxy} ethanimidothioate. 14. Composition according to item 10, characterized in that it is an active ingredient Methyl-N-> L ( { L-isopropyl (4,4,6-trimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl) amino-thio-methylamino) -carbonyl-hexanoimidethio-thioate contains. 15. Composition according to item 11, characterized in that it is active as an ingredient Me t hy 1-Έ - {[* ( "cyclohexyl5,5-dimethyl-2-thioxo ~ 1,3,2 dioxaphosphorinane _T ~ 2 ~ yl {[) amino] thiojmethylamino) carbonyl] 7 oxyiäthanimidothioat, Methyl N - / [({[cyclohexy] (5,5-diethyl-2-thioxo-1,3,2- 16 »agent according to one of the points 12 to 15, characterized in that it contains as an aid or carrier easily diapergierbares aid or an easily dispersible carrier» 17. Composition according to item 16, characterized in that it contains water as an aid or carrier 18. Composition according to item 17, characterized in that it additionally contains a surface-active agent and a finely divided solid. 19. Composition according to item 16, characterized in that the concentration of active ingredient is 0.5 to 75 % . 20, A process for the preparation of N- [_ (phosphinyl) -anilino-thio and E- (phosphinothioyl-amino) -thio-methylcarbamaten of the general formula: